WO2005053404A1

WO2005053404A1 - Fungicide mixtures based on benzamidoxime derivatives

Info

Publication number: WO2005053404A1
Application number: PCT/EP2003/013183
Authority: WO
Inventors: Eberhard Ammermann; Reinhard Stierl; Ulrich Schöfl; Siegfried Strathmann; Klaus Schelberger; Maria Scherer; Egon Haden
Original assignee: Basf Aktiengesellschaft
Priority date: 2003-11-24
Filing date: 2003-11-24
Publication date: 2005-06-16
Also published as: AU2003289891A1

Abstract

Fungicide mixtures comprise in the form of active componenets (1) a benzamidoxime derivative of formula (I), wherein a substituent and an index can have the following significance: R is hydrogen, halogen, C1-C4-Alkyl, C1-C4-halogenalkyl, C1-C4-alkoxy or C1-C4-halogenalkoxy, n 1, 2 or 3, and (2) cyprodinil of formula (II) or (3) proquinazid of formula (III) in a synergy effective quantity.

Description

Fungicidal mixtures based on benzamidoxime derivatives

description

The present invention relates to

Fungicidal mixtures containing as active components (1) a benzamide oxime derivative of the formula I.

where the substituent and the index can have the following meanings:

R is hydrogen, halogen, C 1 -C 4 -alkyl, C 1 -C 4 haloalkyl, C 1 -C ₄ alkoxy or C 1 -C ₄ haloalkoxy

n 1, 2 or 3,

and

(2) Cyprodinil of formula II

or

(3) Proquinazide of Formula III

in a synergistically effective amount.

The invention also relates to a process for combating harmful fungi with mixtures of the compound I with at least one of the compounds II to III and the use of the compound I with at least one of the compounds II to III for the production of such mixtures and agents which contain these mixtures.

From EP-A-1017670, benzamide oxime derivatives of the formula I are known.

The compounds II to III, their preparation and their action against harmful fungi are known per se:

Cyprodinil (II): EP-A-0 310 550 Proquinazid (III): WO 97/48684

The object of the present invention was to provide further means for combating harmful fungi and in particular for certain indications.

Surprisingly, it has now been found that this object is achieved with a mixture which comprises benzamide oxime derivatives of the formula I defined at the outset and a fungicidal active compound of the formulas II to III as a further fungicidally active component.

The mixtures according to the invention act synergistically and are therefore particularly suitable for controlling harmful fungi and in particular powdery mildew in cereals, vegetables and vines.

In the context of the present invention, halogen represents fluorine, chlorine, bromine and iodine and in particular fluorine, chlorine and bromine.

The term "alkyl" encompasses straight-chain and branched alkyl groups. These are preferably straight-chain or branched C 1 -C ₄ -alkyl groups. Examples of alkyl groups are alkyl such as in particular methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1, 1-dimethylethyl.

Haloalkyl stands for an alkyl group as defined above which is partially or completely halogenated with one or more halogen atoms, in particular fluorine and chlorine. Preferably 1 to 3 halogen atoms are present, the difluoromethane / - or the trifluoromethyl group being particularly preferred. The above statements on the alkyl group and haloalkyl group apply correspondingly to the alkyl and haloalkyl groups in alkoxy and haloalkoxy.

The radical R in the formula I preferably represents a hydrogen atom.

The mixtures according to the invention contain at least one compound of the formula II to III.

In order to develop the synergistic effect, a small proportion of the benzamide oxime derivative of the formula I is sufficient. Benzamide oxime derivative and ciprodinil or proquinazide are preferably used in a weight ratio in the range from 20: 1 to 1:20, in particular 10: 1 to 1:10.

Mixtures of the benzamide oxime derivative of the formula I with cyprodinil are preferred.

Mixtures of the benzamide oxime derivative of the formula I with proquinazide are preferred.

When preparing the mixtures, preference is given to using the pure active ingredients I to III, to which further active ingredients can be admixed against harmful fungi or against other pests such as insects, arachnids or nematodes or else herbicidal or growth-regulating active ingredients or fertilizers.

The mixtures of the compounds I with at least one of the compounds II to III or the compounds I and at least one of the compounds II to III used simultaneously, together or separately are notable for an outstanding action against a broad spectrum of phytopathogenic fungi the class of Ascomycetes, Basidiomycetes, Phycomycetes and Deuteromycetes. They are partly systemically effective and can therefore also be used as leaf and soil fungicides.

They are particularly important for combating a large number of fungi on various crops such as cotton, vegetables (e.g. cucumber, beans, tomatoes, potatoes and squashes), barley, grass, oats, bananas, coffee, corn, fruit plants, rice, rye, soy , Wine, wheat, ornamental plants, sugar cane and a variety of seeds. They are particularly suitable for combating the following phytopathogenic fungi: Blumeria graminis (powdery mildew) on cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin plants, Podosphaera leucotricha on apples, Uncinula necator on vines, Puccinia species on cereals, Rhizoonia species, Cotton anonia Rice and lawn, Ustilago species on cereals and sugar cane, Venturia inaequalis (scab) on apples, Helminthosporium species on cereals, Septoria nodorum on wheat, Botrytis cinera (gray mold) on strawberries, vegetables, ornamental plants and vines, cercospora arachidicola on peanuts, Pseudocercosporella herpotrichoides on wheat and barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Plasmopara viticola on vines, Pseudoperonospora species in hops and cucumbers, Alternaria species on vegetables and fruit, Mycosphaerella species in Ban Fusarium and Verticillium species.

The mixtures according to the invention can particularly preferably be used to control powdery mildew fungi in cereal, vine and vegetable crops and in ornamental plants.

The compound I and at least one of the compounds II to III can be applied simultaneously, that is jointly or separately, or in succession, the sequence in the case of separate application generally not having any effect on the control success.

The application rates of the mixtures according to the invention, especially in the case of agricultural crop areas, are from 0.01 to 8 kg / ha, preferably 0.1 to 5 kg / ha, in particular 0.5 to 3.0 kg / ha, depending on the type of effect desired ,

The application rates for the compounds I are 0.01 to 2.5 kg / ha, preferably 0.05 to 2.5 kg / ha, in particular 0.1 to 1.0 kg / ha.

The application rates for the compounds II to III are accordingly from 0.01 to 10 kg / ha, preferably 0.05 to 5 kg / ha, in particular 0.05 to 2.0 kg / ha.

In the case of seed treatment, application rates of the mixture of 0.001 to 250 g / kg of seed, preferably 0.01 to 100 g / kg, in particular 0.01 to 50 g / kg, are generally used.

If pathogenic harmful fungi are to be combated for plants, the compounds I and at least one of the compounds II to III or their mixtures of the compounds I and at least one of the compounds are administered separately or together Compounds II to III by spraying or dusting the seeds, plants or soils before or after sowing the plants or before or after emergence of the plants.

The fungicidal synergistic mixtures according to the invention or the compound I and at least one of the compounds II to III can be used, for example, in the form of directly sprayable solutions, powders and suspensions or in the form of high-strength aqueous, oily or other suspensions, dispersions, emulsions, oil dispersions, Pastes, dusts, scattering agents or granules are prepared and used by spraying, atomizing, dusting, scattering or pouring. The form of application depends on the intended use; in any case, it should ensure as fine and uniform a distribution of the mixture according to the invention as possible.

The formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants, and in the case of water as diluent other organic solvents can also be used as auxiliary solvents. The following are essentially considered as auxiliaries: solvents such as aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), ketones (e.g. cyclohexanone), a ine (e.g. Ethanolamine, dimethylformamide) and water; Carriers such as natural stone powder (e.g. kaolins, clays, talc, chalk) and synthetic stone powder (e.g. highly disperse silica, silicates); Emulsifiers such as non-ionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite liquors and methyl cellulose.

Alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, e.g. Lignin-,

Phenolic, naphthalene and dibutylnaphthalenesulfonic acid, as well as fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols or fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with Condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenol or tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol, ethoxylated polyethylenetholeoxy polyethylenethoxyoxyethoxyalkylene glycol, ethylenedoxyloxyalkylene glycol, ethylenedoxyloxyethylene ethoxylated polyether - acetate, sorbitol ester, lignin sulfite waste liquor or methyl cellulose.

Powders, materials for broadcasting and dusts can be prepared by mixing or jointly grinding the compound I or II to III or the mixture of the compounds I and at least one of the compounds II to III with a solid carrier.

Granules (e.g. coated, impregnated or homogeneous granules) are usually produced by binding the active ingredient or ingredients to a solid carrier.

Mineral earths such as silica gel, silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, boluses, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics and fertilizers are used as fillers or solid carriers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.

The formulations generally contain 0.1 to 95% by weight, preferably 0.5 to 90% by weight, of one of the compounds I or II to III or the mixture of the compounds I and at least one of the compounds II to III. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR or HPLC spectrum).

The compounds I or II to III, the mixtures or the corresponding formulations are used in such a way that the harmful fungi, their habitat or the plants, seeds, soils, areas, materials or spaces to be kept free by them are mixed with a fungicidally effective amount of the mixture, or the compounds I and at least one of the compounds II to III treated separately.

The application can take place before or after the infestation by the harmful fungi.

Examples of such preparations that contain the active ingredients are:

I. a solution of 90 parts by weight of the active ingredients and 10 parts by weight of N-methylpyrrolidone, which is suitable for use in the form of tiny drops;

II. A mixture of 20 parts by weight of the active ingredients, 80 parts by weight Parts of xylene, 10 parts by weight of the adduct of 8 to 10 mol of ethylene oxide and 1 mol of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 5 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil; a dispersion is obtained by finely distributing the solution in water;

III. an aqueous dispersion of 20 parts by weight of the active ingredients, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil;

IV. An aqueous dispersion of 20 parts by weight of the active ingredients, 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction with a boiling point of 210 to 280 ° C. and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole castor oil;

V. a mixture of 80 parts by weight of the active ingredients, 3 parts by weight of the sodium salt of diisobutylnaphthalene-1-sulfonic acid, 10 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite blue acid and 7 parts by weight, ground in a hammer mill. Dividing powdered silica gel; a spray mixture is obtained by finely distributing the mixture in water;

VI. an intimate mixture of 3 parts by weight of the active ingredients and 97 parts by weight of finely divided kaolin; this dust contains 3% by weight of active ingredient;

VII. An intimate mixture of 30 parts by weight of the active ingredients, 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel; this preparation gives the active ingredient good adhesion;

VIII. A stable aqueous dispersion of 40 parts by weight of the active ingredients, 10 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts by weight of silica gel and 48 parts by weight of water, which further ver - can be thinned;

IX. a stable oily dispersion of 20 parts by weight of the active ingredients, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 20 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 88 Parts by weight of a paraffinic mineral oil.

example

The synergistic effect of the mixtures according to the invention can be demonstrated by the following experiments: The active ingredients are prepared separately or together as a 10% emulsion in a mixture of 63% by weight cyclohexanone and 27% by weight emulsifier and diluted with water in accordance with the desired concentration.

The evaluation is carried out by determining the affected leaf areas in percent. These percentages are converted into efficiencies. The efficiency (W) is determined according to Abbot's formula as follows: α W = (1 -) -100 R

α corresponds to the fungal attack of the treated plants in% and ß corresponds to the fungal attack of the untreated (control) plants in%

With an efficiency of 0, the infection of the treated plants corresponds to that of the untreated control plants; at an efficiency of 100, the treated plants showed no infection.

The expected efficacies of the active ingredient mixtures were calculated using the Colby formula [R.S. Colby, Weeds 15, 20-22 (1967)] and compared with the observed efficiencies.

Colby formula: E = x + y - x-y / 100

E expected efficiency, expressed in% of the untreated control, when using the mixture of active ingredients A and B in concentrations a and bx the efficiency, expressed in% of the untreated control, when using active ingredient A in concentration ay, the efficiency, expressed in% of the untreated control when using the active ingredient B in the concentration b

Example of use 1 - Activity against powdery mildew caused by Erysiphe [syn. Blumeria] graminis forma specialis. tritici

Leaves of "Kanzler" wheat seedlings grown in pots were sprayed to runoff point in aqueous suspension in the combination of active ingredients specified below. The suspension or emulsion was prepared from a stock solution with 10% active ingredient in a mixture consisting of 70% cyclohexanone, 20% wetting agent and 10% emulsifier. 24 hours after the spray coating has dried on, spores of powdery mildew (Erysiphe [syn. Blumeria] graminisforma specialis. Tritic) stäubt. The test plants were then placed in the greenhouse at a temperature between 20 and 24 ° C and 60 to 90% relative humidity. After 7 days, the extent of mildew development was determined visually in% infestation of the entire leaf area.

applications

The active substances were prepared separately or together as a stock solution with 0.25% by weight of active substance in acetone or

DMSO. 1% by weight of emulsifier Uniperol® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) was added to this solution and diluted with water to the desired concentration.

Example of use 1 - Activity against powdery mildew caused by Erysiphe [syn. Blumeria] graminis forma specialis. tri tici]

Leaves of "Kanzler" wheat seedlings grown in pots were sprayed to runoff point with an aqueous suspension in the active compound concentration given below. The suspension or emulsion was prepared as described above. 24 hours after the spray coating has dried on with spores of wheat powdery mildew {Erysiphe [syn. Blumeria] graminis forma specialis. tri tici) pollinated. The test plants were then placed in a greenhouse at temperatures between 20 and 24 ° C and 60 to 90% relative humidity. After 7 days, the extent of mildew development was determined visually in% infestation of the entire leaf area.

The visually determined values for the percentage of leaf areas affected were converted into efficiencies as% of the untreated control. Efficiency 0 is the same as in the untreated control, efficiency 100 is 0%. The expected efficacies for active compound combinations were determined using Colby's formula (Colby, SR (Calculating synergistic and antagonistic responses of herbicide Combinations ", Weeds, 15, pp 20 - 22 determines 1967) and compared with the observed _efficacies..

The results of the experiment show that the observed efficiency in all mixing ratios for the combination claimed by us clearly shows the synergism according to the Colby formula.

Comparative Experiment 2 - Protective activity against cucumber mildew caused by Sphaerotheca fuliginea

Leaves of cucumber seedlings of the "Chinese snake" variety, grown in pots, were sprayed in the cotyledon stage with an aqueous suspension in the active ingredient concentration given below to runoff. The suspension or emulsion was prepared as described above. 20 hours after the spray coating had dried on, the plants were inoculated with an aqueous spore suspension of cucumber powdery mildew (Sphaerotheca fuliginea). The plants were then cultivated in a greenhouse at temperatures between 20 and 24 ° C. and 60 to 80% relative atmospheric humidity for 7 days. The extent of mildew development was then determined visually in% of the cotyledon area. The visually determined values for the percentage of leaf areas affected were converted into efficiencies as% of the untreated control. Efficiency 0 is the same as in the untreated control, efficiency 100 is 0%. The expected efficacies for combinations of active substances were determined using the Colby formula (Colby, SR (Calculating synergistic and antagonistic responses of herbicide combinations ", Weeds, 15, pp. 20-22, 1967) and compared with the observed efficacies.

Claims

claims

Fungicidal mixtures containing as active components

[1) a benzamide oxime derivative of the formula I.

where the substituent and the index can have the following meanings: R is hydrogen, halogen, -CC ₄ -alkyl, -C-C ₄ -haloalkyl, -C-C ₄ -alkoxy or -C-C ₄ -haloalkoxy n 1, 2 or 3 , and

(2) Cyprodinil of formula II

or

(3) Proquinazide of Formula III

in a synergistically effective amount.

2. Fungicidal mixture according to claim 1, wherein in the formula I the radical R is hydrogen.

3. Fungicidal mixture according to claim 1, characterized in that the weight ratio of the benzamide oxime derivative of the formula I to the respective compounds of the formulas II to III is 20: 1 to 1:20.

4. A method for combating harmful fungi, characterized in that the harmful fungi, their habitat or the plants, seeds, soils, surfaces, materials or spaces to be kept free of them are treated with the fungicidal mixture according to claim 1.

5. The method according to claim 4, characterized in that the compound of the formula I according to claim 1 and at least one compound of the formula II to III according to claim 1 are applied simultaneously, that is jointly or separately, or in succession.

6. The method according to claim 4 or 5, characterized in that the fungicidal mixture or the compound of formula I with at least one compound of formula II to III according to claim 1 in an amount of 0.01 to 8 kg / ha.

7. fungicidal compositions comprising the fungicidal mixture according to claim 1 and a solid or liquid carrier.